CN1756727B - Process for the production of alkylaromatics - Google Patents
Process for the production of alkylaromatics Download PDFInfo
- Publication number
- CN1756727B CN1756727B CN2004800055085A CN200480005508A CN1756727B CN 1756727 B CN1756727 B CN 1756727B CN 2004800055085 A CN2004800055085 A CN 2004800055085A CN 200480005508 A CN200480005508 A CN 200480005508A CN 1756727 B CN1756727 B CN 1756727B
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- China
- Prior art keywords
- alkene
- stream
- product
- alkylator
- benzene
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 144
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 45
- 238000004821 distillation Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- -1 alkyl aromatic compound Chemical class 0.000 claims description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 238000010555 transalkylation reaction Methods 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 230000029936 alkylation Effects 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 claims description 3
- 241000282326 Felis catus Species 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012013 faujasite Substances 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 229940100198 alkylating agent Drugs 0.000 claims 4
- 239000002168 alkylating agent Substances 0.000 claims 4
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 abstract 3
- 239000005977 Ethylene Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910000975 Carbon steel Inorganic materials 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 239000010962 carbon steel Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011435 rock Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000521257 Hydrops Species 0.000 description 4
- 206010030113 Oedema Diseases 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- JREJWHNDQOGSQT-UHFFFAOYSA-N 1,2,3,4,5-pentaethylbenzene Chemical compound CCC1=CC(CC)=C(CC)C(CC)=C1CC JREJWHNDQOGSQT-UHFFFAOYSA-N 0.000 description 1
- FEWANSQOXSIFOK-UHFFFAOYSA-N 1,2,3,4-tetraethylbenzene Chemical compound CCC1=CC=C(CC)C(CC)=C1CC FEWANSQOXSIFOK-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- NIUAGEVCVWHMTA-UHFFFAOYSA-N 5-(4-iodophenyl)-1-(4-methylsulfonylphenyl)-3-(trifluoromethyl)pyrazole Chemical compound C1=CC(S(=O)(=O)C)=CC=C1N1C(C=2C=CC(I)=CC=2)=CC(C(F)(F)F)=N1 NIUAGEVCVWHMTA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241001125048 Sardina Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
Abstract
A process for producing an alkylaromatic compound includes contacting a dilute olefin feed with a lean oil stream containing aromatic compound and alkylaromatic compound in an absorption zone to provide an alkylation reaction stream containing aromatic compound, alkylaromatic compound and olefin. The alkylation reaction stream is reacted under alkylation reaction conditions in an alkylation reaction zone to provide an effluent containing the aromatic compound and alkylaromatic compound. The effluent of step is separated into the Jean oil stream which is recycled to the absorption zone and a product portion from which an alkylaromatic product is recovered.
Description
Technical field
The present invention relates to prepare the alkylation process of alkyl aromatics, especially relate to by ethene and benzene and under the condition that zeolite catalyst exists, prepare ethylbenzene from alkene and aromatic hydrocarbon.
Background of invention
The several different methods that alkylating by benzene and alkene prepares alkylbenzene is known in the art.The alkene of common use is ethene and propylene.The alkylating of benzene and ethene produces ethylbenzene.The alkylating of benzene and propylene produces isopropyl benzene.
Alkylbenzene is an important chemical material such as ethylbenzene and isopropyl benzene (cumene).Especially, ethylbenzene is common to be used to prepare vinylbenzene, and it can polymerization produce polystyrene, and isopropyl benzene can be used as the additive of superoctane fuel.Or be used to prepare phenol and acetone.
Multiple preparation alkylbenzene, the method that comprises ethylbenzene is well-known, can prepare by the alkylating of benzene as described below and ethene:
C
6H
6+C
2H
4→C
6H
5C
2H
5
Alkylation is normally used for preparing diethylbenzene and the ethylating benzene of other higher degree continuously.Following reaction is typical:
C
6H
5C
2H
5+C
2H
4→C
6H
4(C
2H
5)
2
Other linked reaction takes place than low degree ground, produces such as butylbenzene the material of diphenylethane and higher-boiling compound.Can distillating mixture reclaim ethylbenzene, the ethylating benzene of benzene and higher degree, and the ethylating benzene of higher degree can carry out transalkylation with benzene and forms other ethylbenzene.The method that relates to alkylated reaction is disclosed in people's such as Sardina the United States Patent (USP) 5,003,119, and it is incorporated herein by reference herein.
For example, alkylated reaction can occur in the single fixed-bed reactor, and can adiabatic take place, and promptly being enough to keep under the operating pressure of reactor content in liquid phase on zeolite catalyst, does not supply indirect heating or cooling.In liquid phase, react than catalyzer more effective in gas phase and need be less.Reaction can be carried out with series connection multiple catalyst bed, and for example, benzene can charging can distinguish charging to each catalyst bed for first catalyst bed and ethene.Can use this multistage to inject ethene, because it provides the ratio of high local benzene and ethene to be used to improve selectivity of product in catalyst bed, the action time of purity and extended catalyzed dose.Design variable that can the conditioned reaction device guarantees that the optimum temperuture of each catalyst bed distributes, and causes that the catalyzer working hour prolongs and makes minimum by-products.
Though high-purity ethylene is a preparation alkyl aromatics ideal, it is prepared more expensive than the ethene with dilution.The ethene in dilution source is easier to obtain, thereby and alkylator can be shaped in many ways to optimize and prepare alkyl aromatics by charging different concns ethene.Yet, be not suitable for preparing alkyl aromatics because the non--ethylene component in charging at suitable pressure, is insoluble to alkylator less than under the 1500psig usually with the ethylene concentration charging ethene that is lower than about 70mol%.This causes alkylator in gas phase operation, the lower and more catalyzer of consumption rate liquid phase alkylation reaction of efficient.If even comprise that the ethylene feed that is higher than the 70mol% ethylene concentration comprises that also a large amount of inert low molecular weight impurities (it does not still have relative low boiling point with catalyst reaction) is unsuitable for preparing alkyl aromatics, described low molecular weight impurities is for for example, hydrogen, methane, ethane, nitrogen, carbonic acid gas, carbon monoxide and more not general butane and pentane.The about 5mol% or the hydrogen of a large amount more, methane, nitrogen, carbonic acid gas and/or carbon monoxide especially have problem, because these lower boiling low molecular weight impurities make them especially be difficult to be dissolved in alkylator.
Therefore, need effective alkylated aromatic hydrocarbon, form the method for alkyl aromatics such as ethylbenzene such as benzene.Need to utilize the alkene in dilution source in addition, olefin waste is minimized and during alkylated reaction, reduce the method for catalyst consumption amount such as ethene.
Summary of the invention
The invention provides the method for preparing alkyl aromatic compound.This method comprises that (a) with the lean oil flow that contains aromatic substance and alkyl aromatic compound the alkene charging of dilution is provided provide and contains aromatic substance in absorption band, the alkylated reaction of alkyl aromatic compound and alkene flows; (b) under alkylation reaction condition in the alkylated reaction band alkylated reaction stream of reactions steps (a) effluent that contains aromatic substance and alkyl aromatic compound is provided; (c) effluent of step (b) is separated into the lean oil flow and the product part of the absorption band that is recycled to step (a); And (d) from the partially recycled alkyl aromatic hydrocarbon product of the product of step (c).
The present invention has improved known method by alkene and the aromatic hydrocarbon reaction efficient production alkyl aromatics from relative dilution source.
Description of drawings
Fig. 1 is the schematic flow diagram of preparation alkyl aromatics preferred flow.
Detailed description of the preferred embodiments
The present invention is suitable for extremely wide territory ethylene feed concentration, the application of the input concentration from about 95mol% or higher ethylene concentration to low ethylene concentration to about 3mol%.The present invention also is applicable to the application that utilizes the ethylene feed that comprises a large amount of low molecular weight impurities.Therefore, the present invention is particularly useful for containing have an appointment 70mol% or ethene still less, or the low molecular weight impurities of about 5mol% or greater concn, or the ethylene feed of the two, i.e. charging is not suitable for the situation of known alkylation process usually.
In a preferred method of the invention, alkyl aromatics, can be by the preparation of following process such as ethylbenzene: in the future such as from steam cracker, cat cracker, FCC (fluid catalytic cracking) equipment, refinery, the ethene steam feed in coker or other source (for example, 3-95mol%) give resorber and contact with the chemical flow that absorbs most of ethene by charging, separating hydrogen gas and other inert low molecular weight impurities, such as, methane for example, ethane, nitrogen, carbonic acid gas and carbon monoxide, and more not general butane and pentane be used to be transferred to vent scrubber are transported to the ethene that absorbs therein the alkylator with the benzene reaction then.
With reference to figure 1, ethylene raw is fed to vent absorber 104 by pipeline 102.In resorber 104, most of ethene is absorbed in " poor " the oil stream (that is, being substantially free of the stream of ethene) that contains benzene and ethylbenzene.
Resorber can be the unit absorber of tower tray or packed absorber or packed tower tower tray, and can about 6 ℃ to about 100 ℃ preferred temperature, more preferably between about 10 ℃-20 ℃; And the preferred pressure of about 0-50bar, more preferably from about operate under the pressure between the 10-30bar.Resorber is operated with steam continous way (being gas phase), and can have from 5 to 150 distillation tower trays.The tower tray number of selecting for use is generally 40.The distillation tower tray can be a valve, and stream pipe or other type fall more in sieve.Resorber have with the similar high hydrops situation of the embodiment of the invention under to fall stream pipe tower tray be preferred more.The hydrops of resorber is generally from 10 to 60 gallons every square feet, preferably about 45 gallons every square feet.Resorber can also design filler at random or regular.The distillation level that is provided by filler can be from 4 to 75, preferably 15.Resorber 104 has and comprises that preferred jet between 1.1 and 1.75 overflows safety coefficient, and preferred about 1.35 jet overflows the working parameter of safety coefficient.Resorber 104 has coefficient of combination between about 0.5 to about 1.0 for this system, and preferably about 0.85.Resorber utilizes the carbon steel of standard to make.Do not need to use alloy such as stainless steel.The resorber tower tray is to be made by carbon or stainless steel.If the use filler can be carbon or stainless steel.
Can comprise one or more inert low molecular weight impurities and/or other impurity, hydrogen for example, nitrogen, methane, ethane, propane, carbonic acid gas, carbon monoxide, butane, pentane, hexane, water, non--aromatic hydrocarbon, benzene, toluene, ethylbenzene and one or more polyphenylethyl (PEBs) are such as diethylbenzene, the steam of triethylbenzene etc. is delivered to vent scrubber 108 by pipeline 106, and the aromatic hydrocarbon that wherein is mainly benzene and PEB is reclaiming with PEB stream period of contact and is being delivered to transalkylator 112 by pipeline 110.
Vent scrubber can be tower tray or packed vent scrubber, and can be at about 6 ℃ to about 125 ℃, more preferably from about the preferred temperature between 10 ℃-40 ℃; And about 0-50bar, operate under the pressure between more preferably about 10-30bar.Vent scrubber is operated with the steam continous way.Vent scrubber can have 5 to 100 distillation tower trays.The tower tray number of selecting for use is generally 20.The type of distillation tower tray can be a valve, and stream pipe or other type fall more in sieve.Preferred tray type is a valve.The hydrops of vent scrubber is generally from every square feet about 0.1 to about 5 gallons.Preferred hydrops is every square feet about 0.5 gallon.Vent scrubber can also design filler at random, for example, and such as Pall ring filler or IMTP filler (Koch Engineering Co.Inc., Wichita, dumped packing KS) or structured packing.The number of the distillation level that is provided by filler can be 4 to 75.Preferred progression is generally 10.Preferred working parameter comprises that more preferably about 1.25 jet overflows safety coefficient between about 1.1 and about 1.75.The coefficient of combination of this system can be from about 0.5 to about 1.0, and be preferably about 1.0.Vent scrubber utilizes the carbon steel of standard to make.Do not need to use alloy such as stainless steel.Vent scrubber trays can be made up by carbon or stainless steel.When using filler, can be carbon or stainless steel.
Usually, hydrogen, methane, ethane, water and a spot of C
6Non--aromatic hydrocarbon and benzene are flowed out by circuit 130 by vent scrubber 108.Do not absorb the ethene in the lean oil flow in the resorber 104,, flow out resorber and very small amount of can being recovered in the vent scrubber 108 yet by the pipeline in the overhead vapours 106 preferably less than the 0.1mol% that is conveyed into resorber ethene.
From the effluent of resorber 104, " richness " oil that contains high-level relatively ethene contains the 60wt% that has an appointment usually to about 90wt%, the preferably benzene of about 80wt%; About 5wt% is to about 40wt%, the preferably ethylbenzene of about 15wt%; And about 0.1wt% preferably at least about the ethene of 1wt%, depends on the purity in ethene source to about 5wt% to a certain extent; And be generally some diethylbenzene, ethane, methane and hydrogen.Rich oil flows out resorbers by pipeline 116, and the lean oil flow in the pipeline 124 heats by alkylator heater 120 before entering alkylator reactor 122 then in alkylator feed/effluent interchanger 118 in pipeline 116.Oil rich stream in interchanger 118 by the cooling from about 200 ℃-250 ℃ to about 20 ℃-100 ℃ lean oil flow, be heated to about 100 ℃-250 ℃ temperature out from about 10 ℃-100 ℃ temperature in.These temperature can change in mode well known in the art and optimize energy balance.For example, save energy cost, under the relatively cheap situation of energy, save facility investment thereby perhaps can fully remove interchanger thereby big interchanger can be used to transmit a large amount of heat between stream.Alkylator heater 120 is operated to about 250 ℃ temperature at about 175 ℃.
Alkylator 122 preferably contains at least a loose catalyzer such as zeolite, for example, and zeolite BEA (β) zeolite MWW, zeolite Y, mordenite catalyst, MFI catalyzer, faujasite zeolite catalyst; Perhaps arbitrary other is suitable for the fixed-bed reactor of bed of the arbitrary combination of the molecular sieve catalyst of liquid-phase alkylation or above-mentioned catalyzer.Preferred zeolite BEA.Reactor is with thermal insulation, topping up, and monophasic mode is operated.Alkylator can be on-stream or down-flow reactor.Dirty is preferred structure.Alkylator 122 is preferably at about 150-300 ℃, more preferably under about 180-250 ℃ temperature; About 150-2,000psig, the more preferably pressure of about 300-1000psig operation down; Have about 2-1,000, the typical liquid hourly space velocity (LHSV) of about 4-100 more preferably.Aromatic hydrocarbon and olefin ratio are generally from about 1.0 to about 10, preferably about 1.5 to about 3.5.Alkylator 122 can be operated in liquid phase, because rich oil contains few hydrogen or other inert low molecular weight impurities, for example, methane, ethane, carbonic acid gas, carbon monoxide, nitrogen or the like is because they separate in resorber 104 as mentioned above and are delivered to vent scrubber 108 by the overhead vapours in the pipeline 106.These gases of removing resorber 104 are very important, because it has reduced required pressure in the alkylator 122, carry out thereby make to be reflected in the liquid phase, and usually more wish liquid-phase alkylation because it is more effective and need the catalyzer that lack relatively than gas-phase reaction.Preferably, phenyl in the alkylator 122 (that is, benzene) and ethyl ratio are between about 1.5 to 1, and more preferably about 2.75 to 1 and between about 10 to 1, it will produce good catalyst selectivity, i.e. high yield and stability.Can in alkylation operation, add water and improve productive rate.Water concentration maintains 0ppm between about 1500ppm, and about 500ppm is preferred.The conversion of ethene is completely basically in this reaction.
As mentioned above, alkylator 122 can dirty or last stream mode be operated, although here the example of Lun Shuing is with downward stream mode operant response device.By alkylator have an appointment 1psi and about 15psi, the preferably pressure drop of about 5psi.Preferably from about 5wt% of alkylator to about 99wt%, more preferably about 75wt% extremely the oil-poor of about 95wt% passes through alkylator feed/effluent interchanger 118 after pipeline 124 imports the top of resorbers 104, here, cool off against refrigerant against absorber bottom (rich oil) cooling and by absorber cooler 126.Oil-poorly be cooled between about 6 to about 100 ℃ preferably about 12 ℃.In order to control the temperature rise in the alkylator 122, a part of lean oil flow can be randomly in known manner by recirculation line 125 recirculation in the pipeline 124, and described recirculation line 125 is with the resorber 104 of some the oil-poor introduction pipe lines 116 in the pipeline 124 and any point between the alkylator 122.Recirculation line 125, perhaps pipeline 116 can randomly comprise water cooler 127, further controls the temperature rise in the alkylator 122.Thereby those skilled in the art can specifically be provided with at an easy rate and adjust make limit of temperature rise control to less than about 10 ℃ so that keep The optimum reaction conditions.Narrower temperature range is with optimized choice, and minimum byproduct forms and reduce catalyst deactivation.The remaining lean oil flow of alkylator 122 is transported to benzene distillation tower 132 by pipeline 128.
Randomly, alkylator 122 can comprise that the bed of a plurality of spaced stacked arrangement is to form the alkylated reaction band of continuous level.The polyene hydrocarbon opening for feed can lay respectively at different levels between.For example, high purity polymer grade ethylene (about 100mol% is to the purity of about 70mol%) can randomly directly add to a plurality of alkylator (not shown)s one or multistage, between institute's consumption preferably maintains about 10 to 1 with the ratio of alkene in the alkylator and aromatic hydrocarbon (for example benzene) and between about 30 to 1, more preferably about 30 to 1, it will produce good catalyst selectivity, i.e. high yield and stability.For example, can use six alkylator, wherein Xi Shi ethene reacts in first and high-purity ethylene is fed to subsequently 5 beds.At arbitrary or all bed places, the stream that leaves alkylator bed can cool off before the high-purity ethylene that adds other.Extra ethene amount of adding is approximately identical with the ethene amount of reacting in external crucible.This method maintains liquid phase and anti-devaporation with the liquid stream in the alkylator.This causes effective utilization of catalyzer and total preparation cost will be minimized.In these cases, preferably, the stream in the alkylator is cooled to about 200 ℃ by the process flow that produces steam or heating and add the inside of the position of polymer grade ethylene or position before.This extra step will further reduce total preparation expense.
In another optional arrangement, may contain a large amount of ethane and relatively in a small amount the lean oil flow in the pipeline 124 of ethene can be introduced into ethane distillation tower (not shown).The result of this optional step will be oil-poor from the bottom recovery of ethane distillation tower, and it will be introduced into resorber 104 and reclaim the ethane at ethane distillation tower top in addition.The ethane that reclaims will comprise the methane of relative a small amount of and be particularly useful for thermal cracker.
Get back to vent scrubber 108, in preferred embodiments, comprise mainly that from the aromatic hydrocarbon of vent scrubber 108 about 4 parts of benzene are introduced into transalkylator 112 to about 1 part of PEB and by pipeline 110.Usually pipeline 110 will comprise well heater 111 and transalkylator 112 in the point of crossing of pipeline 110 and pipeline 184 (describing below), as shown in the figure.The temperature operation of well heater 111 between about 170 ℃ to about 260 ℃, preferred temperature is about 200 ℃.In transalkylator 112, aromatic hydrocarbon reacts and takes place about 50% conversion on catalyzer, and transalkylator 112 is left in its generation, contains the liquid of 5 parts of benzene to about 1 part of PEB of having an appointment.
Pipeline 114 carries this liquid effluent from transalkylator 112 to benzene distillation tower 132.Usually be fed to from the benzene distillation tower 132 more than the oil-poor effluent in the pipeline 128 of alkylator from the effluent of transalkylator 112, although it can be fed to identical position of pipeline 128 or following benzene distillation tower.The feed entrance point of two distillation towers is optimised, and the heat input of benzene distillation tower reboiler 144 described below is minimized.
Preferably alkyl group-transfer device 112 is at about 170-260 ℃, more preferably about 200-250 ℃ temperature range, about 150-2000psig, more preferably operate under the pressure of about 300-600psig, have about 1-1,000, the typical LHSV scope of more preferably about 2-100 scope.Transalkylation reaction occurs in liquid phase, and is adiabatic and be middle temperature basically, promptly has less than about 2 ℃ very small temperature rise.Alkyl group-transfer device 112 can be upper reaches or downflow reactor, preferred downflow reactor.
Fig. 1 has shown the alkylator 122 that is used for from pipeline 128, and the transalkylator in the pipeline 114 112 is separated three distillation procedures of effluent in known manner.Effluent in the pipeline 128 and 114 is introduced into benzene distillation tower 132, and benzene reclaims from thick ethylbenzene product in distillation tower.Benzene distills out at cat head as steam, and it is transported to condenser 136 by pipeline 134, liquefies there and remains in the storer 138.Condenser 136 can produce steam or can heat other process flow, and can use water coolant or air.Working parameter is configured to optimize the energy efficiency of this method.Lean oil flow in the pipeline 124 is drawn and be added into to benzene by pipeline 140, and it is introduced into vent absorber 104.Benzene is got back to lean oil flow so that keep benzene concentration suitable in the pipeline 124, thereby has correct selectivity in alkylator 122.Alkylated reaction is carried out balancing control, and promptly the ratio of aromatic hydrocarbon and alkene is determined single selective.Some benzene in the pipeline 140 can change on pipeline 110 and the transalkylator 112 by pipeline 184.As the situation of alkylator 122, keep the proper concn improvement selectivity of benzene in the transalkylator 112.Fresh benzene can also be added into all places in benzene source 180.The exact position is unimportant for device performance.
Get back to benzene distillation tower 132, pipeline 141 carries the part stream in the pipeline 140, promptly liquid return to the top of benzene distillation tower 132 to keep distillation procedure.The liquid that pipeline 142 carries from the bottom of benzene distillation tower 132 flows to reboiler 144.Steam and perhaps be that a little liquid turns back to benzene distillation tower 132 by pipeline 143.Distillation procedure in the steam driven benzene distillation tower 132.
The remnant of benzene distillation Tata underflow, it contains ethylbenzene, and PEBs and higher-boiling compound are transported to ethylbenzene column 148 by pipeline 146.The typical amount of staying the benzene in pipeline 146 streams arrives about 5000ppm for about 1ppm, and about 500ppm is preferred.
Ethylbenzene column 148 is from polyphenylethyl separate ethylbenzene, i.e. end product.Diethylbenzene concentration in the pipeline 150 arrives between about 50ppm at about 1ppm, preferably about 5ppm.Cat head distilled ethylbenzene vapor stream flows out ethylbenzene column 148 by pipeline 150, and liquefaction and be transported to storer 154 in condenser 152 is taken out as ethylbenzene product by pipeline 156 then.Condenser 152 can produce steam or can heat other process flow, and can use water coolant or air.
Pipeline 157 carries the part stream in the pipeline 156, promptly liquid return to the top of ethylbenzene column 148 so that keep distillation procedure.The liquid that pipeline 158 carries from ethylbenzene column 148 bottoms flows to reboiler 160.Steam and perhaps be that a little liquid turns back to ethylbenzene column 148 by pipeline 159.Distillation procedure in the steam driven ethylbenzene column 148.
Ethylbenzene column tower bottom flow in the pipeline 162, it contains PEBs and higher-boiling compound, is conveyed into PEB distillation tower 164 and is used for separating PEBs from higher-boiling compound (for example, heavy rock asphalt).
PEB distillation tower 164 separates PEBs from heavy rock asphalt, and described heavy rock asphalt can comprise tetraethylbenzene usually, pentaethyl benzene, ditan, 1,1-diphenylethane, 1,2-diphenylethane, the second month in a season-butylbenzene and/or other high boiling aromatic hydrocarbon.Usually, the triethyl-benzene less than about 5wt% disappears in rock asphalt.Heavy rock asphalt takes out by pipeline 170 as PEB distillation tower tower bottom flow.Rock asphalt can further be handled as heat transfer fluid or as fuel.Overhead product PEB steam is delivered to condenser 174 liquefaction and is delivered to storer 176 by pipeline 172.PEB is transported to water cooler 182 by pipeline 178, cooling before introducing vent scrubber 108, and in vent scrubber 108, contact with stream from pipeline 106.Condenser 174 can produce steam or can heat other industrial preparation liquid stream, and can use water coolant or air.
Pipeline 179 carries the part stream in the pipeline 178, promptly liquid return to the top of PEB distillation tower 164 with the maintenance distillation procedure.The liquid that pipeline 166 carries from PEB distillation tower 164 bottoms flows to reboiler 168.Steam and perhaps be that some liquid return PEB distillation tower 164 by pipeline 167.Distillation procedure in the steam driven PEB distillation tower 164.
Though the present invention is described according to some specific embodiment, only should be realized that otherwise deviate from those skilled in the art of the present invention and can carry out various changes and replace its element with equivalent.For example, being used to implement chemical composition of the present invention can be according to the alkene that is used at least, and the chemical ingredients of alkylating aromatic hydrocarbon and olefin feedstock changes.For example, except ethene, employed alkene can comprise that propylene or other comprise the branch or the linear alpha-olefin of 2 at least 20 carbon atoms.The aromatic hydrocarbon that uses can comprise naphthalene, anthracene, phenanthrene and derivative thereof except benzene.Therefore, ethylbenzene, isopropyl benzene and other alkyl aromaticss can be prepared by method of the present invention.
Simultaneously, the various parts of above-mentioned equipment can be for example known with other, alkylator, and transalkylator, resorber and/or distillation tower parts substitute.In addition, many other heat exchangers, heating and cooling configuration also can be used according to the place condition.For example, the steam of air or water cooling and different levels produces and can be used for method of the present invention.
Therefore, purpose of the present invention is not limited to disclosed enforcement particular of the present invention here, but the present invention will comprise all embodiments in all appended claims scopes.
Claims (31)
1. the method for preparing alkyl aromatic compound, this method comprises
(a) in absorption band, under 6 ℃ to 100 ℃ absorption temperature, the alkene charging of dilution is contacted with the lean oil flow that contains aromatic substance and alkyl aromatic compound the alkylated reaction that contains aromatic substance, alkyl aromatic compound and alkene oil rich stream is provided, and the alkene charging of wherein said dilution is available from steam cracker, cat cracker, fluid catalytic cracking equipment, refinery or coker;
(b) in heat transfer regions the alkylated reaction oil rich stream is heated to 150 ℃ to 300 ℃ alkylation temperature, and described heated oil rich stream is incorporated in alkylation reaction zone;
(c) under alkylation reaction condition in the alkylated reaction band alkylated reaction oil rich stream of reactions steps (b) effluent that contains aromatic substance and alkyl aromatic compound is provided;
(d) effluent of step (c) is separated into the lean oil flow and the product part of the absorption band that is recycled to step (a), the lean oil flow of wherein said recirculation is cooled to 6 ℃ to 100 ℃ absorption temperature in heat transfer regions; And
(e) from the partially recycled alkyl aromatic hydrocarbon product of the product of step (d).
2. the aromatic substance that the process of claim 1 wherein is selected from benzene, naphthalene, anthracene, phenanthrene and derivative thereof.
3. claim 1 method, wherein the alkene alkylating agent is selected from ethene, propylene, and other contains the branch or the linear alpha-olefin of 2 at least 20 carbon atoms.
4. the alkyl aromatic compound that the process of claim 1 wherein is selected from alkylbenzene, polyalkylbenzene and composition thereof.
5. the method for claim 4, alkylbenzene wherein is selected from ethylbenzene and isopropyl benzene.
6. the method for claim 4, polyalkylbenzene wherein is selected from diethylbenzene, triethylbenzene, benzene of higher ethylization degree and composition thereof.
7. the process of claim 1 wherein that the alkene charging of dilution has the concentration of olefin of 3mol% to the 95mol% scope.
8. the method for claim 7, wherein Xi Shi alkene charging has the concentration of olefin of 3mol% to the 70mol% scope.
9. the process of claim 1 wherein that the alkene charging of dilution comprises that one or more is selected from following inert low molecular weight impurities: hydrogen, methane, ethane, nitrogen, carbonic acid gas, carbon monoxide, butane and pentane.
10. the method for claim 9, wherein Xi Shi alkene charging has the inert low molecular weight impurities concentration of 5mol% at least.
11. the method for claim 10, wherein Xi Shi alkene alkylating agent charging has the concentration of olefin of 3mol% to the 70mol% scope.
12. comprising, the absorption band that the process of claim 1 wherein is selected from the packed tower resorber, the unit absorber of tower tray resorber and tower tray and packed tower.
13. the method for claim 12, wherein the gas overhead product from resorber is changed over to vent scrubber.
14. the method for claim 12, resorber is wherein operated in gas phase.
15. the process of claim 1 wherein that the alkylation reaction band comprises alkylator.
16. the method for claim 15, alkylator wherein are fixed-bed reactor.
17. the method for claim 16, wherein alkylator comprises that a plurality of beds and a plurality of alkene that lay respectively between the bed enter the mouth.
18. the method for claim 15, alkylator is wherein operated in liquid phase.
19. comprising, the method for claim 15, alkylator wherein be selected from zeolite BEA, zeolite MWW, zeolite Y, mordenite catalyst, the catalyzer of MFI catalyzer and faujasite zeolite catalyst or its combination.
20. the lean oil flow in the step of the process of claim 1 wherein (c) accounts for the 5wt% of step (b) effluent to 99wt%.
21. the method for claim 20, wherein the lean oil flow in the step (c) accounts for the 75wt% of step (b) effluent to 95wt%.
22. the process of claim 1 wherein that recycling step (d) comprises one or more distillation procedure.
23. the method for claim 22, wherein unreacted aromatic substance is recovered in first distillation procedure and the alkyl aromatic hydrocarbon product is recovered in the after-fractionating operation.
24. the method for claim 23, wherein the unreacted aromatic substance of at least a portion is recycled to lean oil flow.
25. the effluent of the step of the process of claim 1 wherein (b) comprises the more alkyl aromatic by product that is recovered in the distillation procedure equally.
26. the method for claim 25, wherein the more alkyl aromatic by product of at least a portion recovery is introduced into vent scrubber to be provided for changing over to the transalkylation reaction stream of transalkylator.
27. the method for claim 26, wherein transalkylation reaction stream is placed under the catalysis transalkylation reaction conditions to form the transalkylation reaction product stream that has higher aromatic hydrocarbon and more alkyl aromatic ratio than transalkylation reaction stream.
28. the method for claim 26, wherein transalkylation reaction product stream is introduced into the operation of reclaiming unreacted aromatic substance and alkyl aromatic compound respectively.
29. the process of claim 1 wherein extra alkene alkylating agent is added alkylation reaction band to step (b).
30. the method for claim 29, wherein extra alkene alkylating agent is highly purified ethene.
31. the step of the process of claim 1 wherein (c) comprises following additional step: the alkylated product stream with the first part of step (b) before the contact zones that first part's alkanisation product flow are recycled to step (a) places the operation of reclaiming ethane.
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| US10/376,683 | 2003-02-28 | ||
| PCT/US2004/005548 WO2004078681A2 (en) | 2003-02-28 | 2004-02-25 | Process for the production of alkylaromatics |
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| CN1756727B true CN1756727B (en) | 2010-07-14 |
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| US (1) | US7238843B2 (en) |
| EP (1) | EP1597217B1 (en) |
| JP (1) | JP4915733B2 (en) |
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- 2003-02-28 US US10/376,683 patent/US7238843B2/en active Active
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2004
- 2004-02-25 CN CN2004800055085A patent/CN1756727B/en not_active Expired - Lifetime
- 2004-02-25 MX MXPA05008716A patent/MXPA05008716A/en active IP Right Grant
- 2004-02-25 KR KR1020057015702A patent/KR101149717B1/en active IP Right Grant
- 2004-02-25 RU RU2005130259/04A patent/RU2322430C2/en not_active IP Right Cessation
- 2004-02-25 CA CA2516898A patent/CA2516898C/en not_active Expired - Fee Related
- 2004-02-25 BR BRPI0407792-0A patent/BRPI0407792B1/en not_active IP Right Cessation
- 2004-02-25 EP EP04714609.7A patent/EP1597217B1/en not_active Expired - Fee Related
- 2004-02-25 AU AU2004218011A patent/AU2004218011B2/en not_active Ceased
- 2004-02-25 WO PCT/US2004/005548 patent/WO2004078681A2/en active Application Filing
- 2004-02-25 JP JP2006508824A patent/JP4915733B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2004078681A2 (en) | 2004-09-16 |
| ZA200506862B (en) | 2006-04-26 |
| KR20050106043A (en) | 2005-11-08 |
| US7238843B2 (en) | 2007-07-03 |
| US20040171899A1 (en) | 2004-09-02 |
| AU2004218011B2 (en) | 2010-02-25 |
| CN1756727A (en) | 2006-04-05 |
| JP4915733B2 (en) | 2012-04-11 |
| EP1597217A2 (en) | 2005-11-23 |
| AU2004218011A1 (en) | 2004-09-16 |
| BRPI0407792B1 (en) | 2014-01-28 |
| CA2516898A1 (en) | 2004-09-16 |
| KR101149717B1 (en) | 2012-06-11 |
| MXPA05008716A (en) | 2005-09-20 |
| EP1597217B1 (en) | 2014-08-06 |
| CA2516898C (en) | 2011-10-11 |
| RU2005130259A (en) | 2006-02-10 |
| JP2006519857A (en) | 2006-08-31 |
| RU2322430C2 (en) | 2008-04-20 |
| WO2004078681A3 (en) | 2004-12-09 |
| BRPI0407792A (en) | 2006-02-14 |
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